Process for treating smelter smoke and extracting values from ores or metallurgical waste products.



No. 875,222. PATENTLD DEC. 31. 1907. s. s. SURENSEN 2 G. 0. WESTBY. PROCESS FOR TREATING SMELTBR SMOKE AND EXTRAGTING VALUES PROM ORES OR METALLURGICAL WASTE PRODUCTS.

APPLICATION FILED JAN. 25. 1906.

3 SHEETS-SHEET 1.

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PATBNTED DEC. 81. 1907. S. S. SURENSEN & G. G. WESTBY. PROCESS FOR TREATING SMELTER SMOKE AND EXTRAUTING VALUES FROM ORBS OR METALLURGICAL WASTE PRODUCTS.

APPLIOATION FILED JAN. 25. 1906.

s SHEETS-M1231 2.

INVENTORS a m B;v fhez'rA Home WITNESSES:

-%- Zgfini/ 6% No. 875,222. PATENTED DEG. 31. 1907. S. S. SURENSBN & G. O. WESTBY. PROCESS FOR TREATING SMELTER SMOKE AND EXTRAOTING VALUES FROM ORES 0R METALLURGICAL WASTE PRODUCTS.

APPLICATION FILED JAN 25. 1906.

3 SHEETS-SHEET 3.

WITNESSES: 0/ a/LNVENTORS A I WW lg gzhindtiomey, f,

fimm WWW Warren srarns @h lt llfihlo STANLEY SEVERIN SORENSEN AND GEORGE G. WESTBY, OF MURRAY, UTAH.

PROCESS FOR TREATING SHELTER SMOKE fiND'EXiIRACTING VALUES FROM ORES OR METALLURGICAL WAFSTE iPROD'UCTS.

Specification of Letters li atent.

Patented Dec. 81, 1907.

Application filed January 25. 1903- S erial H0. 297.920.

To all whom it may concern:

Be it known that We, STANLEY SEVERIN SoRnNsEN and GEORGE CUTLER Wns'rnr, the former a British subjectand the latter a citizen of the United States of America, and residents of Murray, county of Salt Lake, and State of Utah, have invented certain new and useful Improvements in Processes for Treating Smelter Smoke and Extracting Values from ()res or h letallurgical l/Vaste Products, of which the following is a specification.

()ur invention relates to im )rovements in method of and apparatus for the purification of smelter smoke containing injurious or obnoxious gases'or vapors of sulfur arsenic and the like and rendering it harmless to animal and vegetable life; and the recovery of the commercially valuable constituents of ore treatinent Wastes or of ore.

Heretofore it has been the practice to render harmless the smelter smoke arising from various metallurgical operations in the treatment of sulfid ores, such as roasting, smelting, converting or refining, by cooling and scrubbing the smoke with water in various forms of absorption towers or fines, or by means of milk of lime or by magnesium hy-.

drate or carbonate or oxid in apparatus specially designed therefor. Now We have discovered that smelter smoke of the kind described can be more advantageously and economically purified by bringing the said smoke after it issues from the furnaces or other apparatus in which it is generated, directly into contact with suitable and suitably prepared metallurgical wastes such as" slag or tailings or ores under the proper conditions to be hereinafter described, whereby not only is the said smoke puriiicd but the otherwise lost constituents in the said metallurgical Wastes or ores are largely recovered. Our process consists of causing the hot smoke to come into direct and intimate contact with linely divided moistened Wastaproducts such as granulated slag, slag Wool], tailings, or ore, or any combination of said mas terials whereby the sulfur gases in the smoke combine with the bases and metals in the said products. This combination is oi footed in the presence of and through the mediumof water and water vapor whereby sulfates, sulfites, thiosulialies and possibly other tliionous and thionic salts are formed,

which soluble in the presence of the free sulfurous and sulfuric acids simultaneously formed by the smoke. After the formation of the above salts other series of reactions occur whose cause depends on the apparatus used and other working conditions which are variable as for instance the temperature of the smoke, the concentration or percentage of sulfur dioxid, oxygen and water used in this part of the process. These reactions are not of primary importance, but it is preferable to secure a mixture in solution of sulfates, thionous and thionic salts".

v The second step of the process consists in the recovery by precipitation from the solution formed above described of copper and other metals )recipitable as suliids in a mineral acid solution. If the solution from the contact smoke scrubbing apparatus contains gelatinous silica in solution, in order to prevent the precipitation of the latter if the solution be not su'lliciently acid, we add acid, preferably sulfuric acid, to keep the silica in solution and then heat or boil it. The copper and other precipitable metals are thereupon thrown down as sul'lids, by the action oi the reducing salts already present in the liquor. The metals can then be recovered by any of the known processes.

When it is desired to precipitate the last traces of the aforesaid sulfureted metals, a solution of FeS, FeS O,,, and FeSO is added which is obtained by treating metallic iron such as scrap by a solution of sulfurous acid or crude scrubbing liquors containing free S9,. The metals are in this case also recovered from the sulfureted precipitates by any known method.

If desired, the supernatant liquor from the iron compounds may be treated for the pur-- poses of saving the zinc, nickel, cobalt, etc. contained therein, by any of the Well-known methods of treatment, or the liquor may be allowed to run to Waste, as may be most convenient.

Where commercial conditions make it desirable, a liquor containing sulfuric acid is used as a substitute for the acid necessary to retain gelatinous silica in solution, which ii-quoris prepared by adding a solution of ferric sulfate or an oxidized scrubbing liquor to pyrites then adding to the mixture a little sulfurous acid or smoke scrubbing liquor and heating the Whole to promote the reaction which forms H,,SO, according to the equation resiwreasoi a+smo=1treso4+ n era.

The sulfurous acid solution is added by rea son of its availability and the necessity otan acidulatedsolution when heating asolutlon of ferric sulfate, care being taken not to add a suificient amount of the reducing agent to scrubbing interferewith the above reaction.

The sulfurous acid, however, ma be omitted and the sulfuric'acid developed by treating the ites with cold solutions of ferric sulfate.

.At this stage local conditions may render 1t most profitable to discharge and waste the then residual liquor say for instance into the sea. But it may-in other cases be profitable to extract further values or it may be necessary to render it more harmless before allowing it to run to waste. In the latter case the liquor is neutralized, say by calcareousearth or limestone and oxidized and is boiled withthe occasional addition of calcareous earth or limestone as may mation of basic salts. Air is sometimes used in this connection to facilitate and hasteii the oxidation. 'By these means a basic salt of iron is precipitated which is insoluble .in water and which may according to local conditions be itself a marketable roduct.

When it is desired toobtain t e silica separately from the solution from the smoke apparatus the residual liquor is neutralized, after the copper and the other l mixed basic sulfate and separated out.

- lowed to settle out and the supernatant {and thezinc, nickel,

similarly precipitabl'e metals have been precipitated there rom, without oxidizing it and just gently heating by which the bulk of the silica is thr 'cipitate and own down and obtained as a prethe liquor is decanted and further treated for iron salts as above described. After the silica has settled out the su ernatant liquor is withdrawn and completely oxidized by any commercial method, the liquor is then neutralized by the addition of lime,

limestone or calcareous earth and boiledaddr a little of these substances until the hydrate of iron are The precipitate is then alliquor from the precipitated iron compounds cobalt, and other metal therein, removed by treatment in any con- 7 It will thus be seen face of wet and porous slag or ore while at copper by vent liquordeveloped in theapparatus 61 1 '-in the case ofa vertical chamber,

case'sfed into the chamber from the hopper a suitable. source of divided matter is caused to be mixed wit be required to neutralize tently through the any.fresh acidity developed during the forbloc suitable .material is thus gradual the dame time 'certain ofitslvaluable etastituents are extracted, princl ally s lver and e" and the solmeans .ot the smo ployed. la ,i v a. I, l or,thepurpose of carrying outthe above" descr bed process, a variety of a paratus may be employed but-we'prefer, oWever, to make use'of .a

chamber which may be vertical, horizontal or inclined, into which the dust-laden smoke .is' led directly by means of hoppers. The material may be fed from the flues into the apparatus by gravity or in other by meansof Ma'- wormconveyer driven lrom water orsolution produced at aprevious op-- a eration. Where a vertical chamber is used the material is introduced-at the :-top ot'the chamber either with the water or intermlthoppersQfWhen a hone zontal or inclined chamber :is'einployed, vthe sla or ore and water gravitate to the-lower en ofthe chamber and may be discharged intermittently or continuo'usly. The-chamber is provided when statipnary with a series the finelyv of: shelves in its interior carrym powdered slag, ore or other sulta moistened by water or solution and as 1e material same is fed continuously or intermittently power. I The finelyi 95. they with the water hrough the hoppers, 'the.:--

Water being regulated independently' the material falls from shelf to shelf, these being staggered to produce an in the passa e of the smoke around the; sl glves and t When the rotative form of apparatus is used, shelves or projections are provided in the in terior, set at different angles to the circum ferencerin erder to lift and then spill the la. arrested fall without but rough the apparatus? solid material and water. at different points mixing 'cf -gas with the material used. In both forms of apparatus the sla or other ly carried from top to bottom either of the tower or of the chamber by the washing action of the water arid by gravity, and the solvent action of the smoke in combination with the. water and the supply of the fresh solid reagent continually replaces the old or exhausted material. Sometimes apparatus consisting of a combination of the twoforms above described, maybe employed, the smoke passing first through one and then through the other,

thereby securing the advantages of both forms, but in any case it is essential to employ an apparatus which .will cause the smoke to make intimate and direct contact with the wetted particles of the finely divided material, by agitation or movement, so that fresh surfaces'of wetted material 'will constantlybe brought into contact with the through the revolution in order to cause the iso other-convenient manner.-

smoke in the manner effected by the apparatus above described.

Apparatus of the character of that referred to above, is shown in the three sheets of drawings, which are in part of a diagrammatic nature, and which form part of this specification, and in which Figure 1 is a vertical elevation partly in cross section of the apparatus, in which a part of the process is carried out. Fig. 2 is a vertical cross section of the form of apparatus shown in Fig. 1 on the line 3I3 of Fig. 1. Fig. 3 is an end elevation of the form of apparatus shown in Fig. 1. Fig. 4 is a similar vertical section of the same part of the apparatus, with modifications in method of feed and discharge. Fig. 5 is a vertical cross section of the apparatus shown in F 4 on the line 5-5 of said" figure. Fig. 6 is, a vertical elevation partly in section of another form of the apparatus used for carrying out said process on the line 6-6 of Fig. 7; and Fig. 7 is an elevation partly in section of the same part of the apparatus on the line 7-7 of Fig. 6.

Similar nui'nerals refer to similar parts throughout the several views. r

In the drawings Fig. 1 represents a chamber which is horizontal or inclined. The cylinder ends are supported at either end upon the brackets 12, which in turn are mounted upon a table 14, resting upon the blocks 15. One end of this table is capable of being lowered by means of the manipulation of the block 16, which is placed between it and the block 15 at the right hand end of Fig. 1. driving it out, the angle of inclination of the table 14 may be varied. For the purposes of supporting the cylinder 1, the rollers 17 mounted upon suitable supports 18 are provided, which engage with circular bands 1.) upon the exterior surface of the cylinder 1.

Rotary motion is imparted to the cylinder by the driving pulley 20 mounted onv the shaft 21 supported on the blocks 22, or in any The shaft 21 carries a gear wheel 22- which engages with a gear 24 on the exterior surface of the cylinder 1. The ends of the cylinder are open, as shown in .Fig. 1, rotate freely in the heads 3 at either end.

2 is a feed hopper supported on a block 25 at the end of the table which opens into a preferably circular feed pipe 4, which enters the head 3 at the point shown and emerges into the interior of the cylinder 1.

The feed pipe 4 is provided in its interior with a worm'conveyer 5 driven by a pulley 13 attached to the shaft 6 of the worm conveyer, which passes out through suitable stul'ling box 7; the. discharge is effected by means of a similar worm conveyor 8 at the other end of the cylinder 1 which conveyer is mounted upon the shaft 9 and driven by the By driving in the upper block 16 or pulley 1() and placed within a bent cylinder 11, which emerges in one end into the rear end of the cylinder and at the other end into a suitable receptacle 26, which sealed with water or other solution in which the material treated is colle: ted.

A lluc 27 enters the cylinder at opposite end 2 the feed end through which the smoke is admitted to the-'interior, and a suitable llue 2H emerges therefrom at the feed end through which the smoke after treatment can escape.

The interior of the chamber is provided throughout its length with a series of shelves 2!) supported on the brackets 30, and in the center is a continuous series of shelves 3] supported by suitable webs which are not shown, so that the central series of shelves rotate with the chamber. set atdifi'erent angles to the circumference and their object is to spill the material being treated in thin streams through the different These shelves are.

.111 the structure shown in Fig. 4, the material is admitted from the hopper 2 through a manhole 32 in the top of the cylinder and is discharged through a manhole 33 at the other end. The cylinder is supported heretofore, the only difference being that the l'iearings at either end are sufficiently large to enable the smoke to flow in through the hollow center of the bearing 34 and to be dis charged through the hollow center of the bearing 35. The rotary movement is imparted in this case by means of pulley 20, which instead of being placed on a separate driving shaft, is placed on the main shaft of the machine. A stulling box 36 connects the hollow shaft 34 with the pipe 37 in such a way as to effect angular connection and adjustment when the table is raised and lowered.

The shelves 29 in the interior of the chamber are of the same general construction as .those shown in Figs. 1 and 2, but the central shelf 31' is replaced by the shelves 43. The

shelves 29 and 31. and 43 may be of any eonvenient form, and may be set at whatever anmay be found to give the best results.

F 6 and 7 show a vertical tower or flue 50, in which is arranged a number of shelves 57. 52 is a series of hoppers at the base of each of which is a rotary feeder 56 carried on a shaft 55 driven from pulley 54. '53 is a pipe through which water or other solution may enter intermittently and flow from shelf to shelf through the tower, the shelves 57 being arranged staggered to produce an arrested fall without blorkin'g the passage of the smoke through the shelves and through the tower. The water which settles at the bottom ofthe tower at 58 is discharged by the spent 60, a seal being effected by the purifyingsmelter smoke and extracting consisting in preparing and sulfites ahd the nets, consisting in causing such blade 59. 61 is a flue through which the smoke enters and 62 is afiue through which it passes out. I

For precipitati the various products we do so inany suita is form of tanks or vats using preferably wooden construction with lead steam pipes for heating and boilingthe various liquids as required. 1

We claim as our invention:

1. The hereinbefore described process of values from ores or metallurgical waste prod-' ucts consisting in preparing the materials to be treated by-comminuting the same, and thencausin sulfurous smoke to come incontact with tie materials in the presence of moisture or water while they are being agitated, whereby the valuable bases or metals of the slag, are converted into sulfates, thionites, and sulfites by means of the sulfur thionates, dioxids and sulfuric acid of the smoke. 2. The herein described process for purifying smelter smoke and extracting values from ores or metallurgical waste products the materials to be treated by. comminuting thesame and then causing the sulfurous smoke to come into direct contact with the materials in the pres ence of moisture or water while they are be ing agitated, whereby 'the sulfur dioxid and-sulfuric acid of the smoke with the aid of solutions present in the mass resultant from the reactions between the materials being treated and the smoke'combine with the bases, metals and salts of the materials being treated, and ass into solution, sub

stantially as set fort 3; The hereinbefore described process of purifying smelter smoke and extracting values from ores or metallurgical waste products, consisting in causing such ores or products or any mixture thereof, suitably prepared by grinding, shredding, otherwise finely comminuting, to come in a moistened or wet state, into direct and intimate contact with the smoke, by sub stan' tially continuous minutely subdividing agitation or movement of said ores or products.

by means of spilling in fine streams or drops in suitable receptacles whereby fresh surfaces of such ores or products'are exposed at the sulfur dioxid the material tobe treated and become converted into sulfates, thionates, thionites flue dust is extracted, and subsequently reating the residual liquor and undissolved residues for the recovery of the values therein, in any desired manner.

4. The hereinbefore described process of purifying smelter smoke and extracting values from ores or metallurgical waste prodores or prodin suitable receptacles whereby fresh surfaces of such ores or products are exposed at fre uent intervals,- and the sulfur dioxid an" sulfur acid of the smoke with the aid of solutions present in the mass resultant from the reactions between the material being treated and the smoke, combine with being treated and'go' into solution, and sub seguently treating the residual liquor and values therein, in anydesired manner.

with thematerials m the presence of mois ture or water, while they are being agitated,

materials are converted into sulfates, thionates, thionites and sulfites by means of granulating or the sulfur dioxid and sulfuric acid of the smoke, and collecting the valuable residual concentrates left after the solution of the bulk of the material. a

'6. The hereinbefore described process of purifying smelter smoke sla and extracting values from slag, 'slimes, tailings or ores, consisting in preparing the treated by comminuting the same, then causing sulfurous smoke to come in con- ,tact. with thematerials in the presence of moisture or water when they are being agitated whereby the valuable bases or metals of the material are converted into sulfates, thionates, thionites, and sulfites by means of the sulfur dioxids and sulfuric acid' of the smoke, collecting the valuable residual concentrates, evaporatin the solution, finally collecting the residual products. 7. The hereinbefore described'process for purifying smelter smoke and extracting the valuable material from finely divided slag, slimes, tailings or ores, consisting in causing the sulfurous smoke to come into direct contact with the suitably prepared materials to be treatedinthe'presenee of moisture or water, then collecting theliquor which has drained from the purifying apparatus, and finally allowing the precipitates formed to settle together with any silica precipitated, substantially as set forth. a

8. The hereinbefore described process for purifying smelter smoke and extracting the valuable material fmm finely divided slag,

the metals, bases and salts of the materials and issol'uble residues for the recovery of the 5/ The herein described process of'puri.

whereby the valuable bases or metals of the materials to be,

ings or ores, consisting in causing the sul- .furous smoke to come in direct contact with the suitably prepared materials to be treated in the presence of moisture or water, collecting the liquor which is drained from the purifving :mparatu acidifying it and heating it and precipitating the copper therefrom, and subsequently treating the residual liquor for the recovery of the values therein in any desired manner.

10. The hereinbefore described process for purifying smelter smoke and. extracting values from linely divided slag, slimes, tailiugs or ores consisting in causing the sulfurous smoke to come into direct contact with suitably prepared materials to be treated in the presence of moisture orwater, and collecting the liquor which has drained from the purifying apparatus, heating it, and allowing the precipitates formed to settle, substantially as set forth.

11. The hereinbefore described process for purifving smelter smoke and extracting values from finely divided slag, slii'nes, tai lings -or ores ct'msisting in causing the sulfurous smoke to come into direct contact with suitably prepared materials to be treated in the presence of moisture or water and collecting the liquor which has drained from the purifying apparatus, acidifying and heating it and allowing the precipitates formed to settle, substantially as set forth.

12. The hereinbefore. described process for purifying smelter smoke and extracting values from finely divided slag, slimcs, tailings or ores, consisting in causing the sulfurous smoke to come into direct cont-act with suitably prepared materials to treated in the presence of moisture or water, collecting the liquor which. has drained from the purifying apparatus, adding thereto a suitably prtp-u-ed solution. containing sull'uric acid. heating the mixed solutions and allowing the pre ipitates to settle out, substantially as set forth.

13. The hereinbefore described process for purifying smelter smoke, and extracting values from linely divided slag, shines, tailings -.'l' ores, consisting in causing the sulfurous smoke to come into direct contact with suitably prepared materials to be treated in tlnapresence of moisture or water, ccll ctiltg the liquor drained from the purifying a paratus, adding an s ider acid liquor, adding a solution prepared by treating metallic iron with sulfurous acid, or smoke scrubbing liquor containing sulfurous acid. and heating the mixed solutions and allow iug the precipitates formed to settle, substautiall as set forth.

1- The hcreinbefore described process for purifying smelter smoke and extracting values from the linely divided slag, slimes, tailings or ores, consisting in causing the sulphurous smoke to come into direct contact with. suitably prepared materials to be treated in the presence of moisture or water, collecting the liquor drained from the purifying apparatus, adding an acid or acid liquor and a solution containing sulfur salts of iron prepared by the addition of a liquor contain ing sulfurous acid to metallic iron, heating and allowing the metallic precipitates formed to settle out, filtering or decanting the supernatant liquor, then neutralizing or nearly neutralizing the filtrate, and heating the liquor allowing the precipitated silica to settle out, substantially as set forth.

1."). The hereinbefore described process for purifying smelter smoke and extracting values from finely divided slag, slimes, tailings or ores, consisting in causing the sulfurous smoke to come into direct contact with suitably prepared materials to be treated in the rescnce of moisture or Water, collecting the iiquor drained from the purifying apparatus, adding thereto a solution prepared by treating metallic iron with a solution containing sulfurous acid, and heating the mixed solution and allowing the metallic precipitates and silica to settle out, substantially as set forth.

to. The hereinbefore described process for purifyiil'g smelter smoke and extracting values from finely divided slag, slimes, tailings or ores, consisting in causing the sul- .furous smoke to come into direct contact with suitably prepared materials to be treated in the presence of moisture or water, then collecting the liquor drained from the purifying apparatus, then adding an acid or acid liquor and a solution containing sulfur salts of iron prepared by the addition of a liquor containing sulfurous acid to iron, heating and allowing the metallic precipitates formed to settle out, filtering or deranting the supernatant liquor, neutralizing or nearly neutralizing the filtrate, heating the liltrate and allowing the precipitated silic: to settle out, y'vithdrawing the supernatant liquor from the silica and oxidizing the liquor by any known commercial means completely, neutralizing the liquor with lime,limestone or calcareous earth, boiling the liquor adding a little lime, limestoneor calcareous earth from time to time until the mixed basic sulfate and hydrate of iron separates out, allowing the precipitate to settle out, withdrawing the supernatant liquor from the precipite tediroh'eempduhds, in pfesence of two-witnesses, this seven and thereafter treating ithe acid, H 1101': if teenth daypf January, 1906.

desired for zinc, nickel, cobalt, an other S. SEVERIN; SORENSEN, metals by any known method, substantially GEORGECJ WESTBYV 5 as set forth. t Witnesses:

In testimopy', that .we'cleim the foregoing A. A} BIRD as our inventlon, and. have signed our names I DANID. W. MQFEAT. 

